Quantum Chemical Study of the Effect of Precursor Stereochemistry on Dissociative Chemisorption and Surface Redox Reactions During the Atomic Layer Deposition of the Transition Metal Copper

Using quantum chemical calculations, we investigate surface reactions of copper precursors and diethylzinc as the reducing agent for effective Atomic Layer Deposition (ALD) of Cu. The adsorption of various commonly used Cu^(II) precursors is explored. The precursors vary in the electronegativity and conjugation of the ligands and flexibility of the whole molecule. Our study shows that the overall stereochemistry of the precursor governs the adsorption onto its surface. Formation of different Cu^(II)/Cu^(I)/Cu⁽⁰⁾ intermediate complexes from the respective Cu^(II) compounds on the surface is also explored. The surface model is a (111) facet of a Cu₅₅ cluster. Cu^(I) compounds are found to cover the surface after the precursor pulse, irrespective of the precursor chosen. We provide new information about the surface chemistry of Cu­(II) versus Cu­(I) compounds. A pair of CuEt intermediates or the dimer Cu₂Et₂ reacts in order to deposit a new Cu atom and release gaseous butane. In this reaction, two electrons from the Et anions are donated to copper for reduction to metallic form. This indicates that a ligand exchange between the Cu and Zn is important for the success of this transmetalation reaction. The effect of the ligands in the precursor on the electron density before and after adsorption onto the surface has also been computed through population analysis. In the Cu^(I) intermediate, charge is delocalized between the Cu precursor and the bare copper surface, indicating metallic bonding as the precursor densifies to the surface